Personal care compositions that deposit hydrophilic benefit agents

ABSTRACT

A personal care composition comprising a hydrophilic liquid, a structurant for said hydrophilic liquid, a surface active, a lipid, and an aqueous phase; wherein said lipid, said hydrophilic liquid, said structurant, and said surface active form a lipid phase; wherein said hydrophilic liquid, said structurant, and said surface active are connected to said lipid in said lipid phase. These compositions provide improved skin and/or hair moisturization, appearance, aesthetics and skin and/or hair conditioning during and/or after application, and are useful in providing improved deposition to the desired area of the skin and/or hair. The present invention is further directed to a method of using the personal care composition.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.60/564,259, filed Apr. 21, 2004.

FIELD

The present invention relates to the field of personal care compositionsfor improving moisturization and appearance and feel of keratinoussurfaces. More specifically, the invention relates to rinsable personalcare compositions that deposit hydrophilic benefit agents on keratinoussurfaces and provide excellent skin and/or hair moisturization,conditioning, tone, and radiance.

BACKGROUND

Personal care compositions are well known and widely used. Thesecompositions have long been employed to cleanse and moisturize skinand/or hair, deliver actives, hide imperfections and to reduce theoiliness/shine associated with sebum. While the compositions anddisclosures of the prior art provide useful advances in the art ofpersonal care compositions, additionally, there remains the need forimproved personal care compositions that deliver immediate and chronicimprovements in skin and/or hair moisturization, appearance and feel,and will effectively deposit on all parts of the body. The compositionsalso need to be non-greasy and easy to apply.

Some methods of depositing benefit agents commonly used includeencapsulation of hydrophilic materials in a hydrophobic shell that isdispersed in hydrophobic lipid carriers for depositing hydrophilicmaterials on skin and/or hair. However, the deposited hydrophilicmaterials are not able to be readily released onto skin and/or hair toprovide skin and/or hair benefits. The use of water-oil-water emulsionsis another way to potentially deposit hydrophilic materials. However,the instability of these types of products often results in a slow leakof hydrophilic materials into the external aqueous phase, and thereforelow deposition efficiency. Additional methods of depositing benefitagents include absorbing hydrophilic materials into hydrophilic porousparticles for slow release of the hydrophilic material for leave-onapplication. However, hydrophilic particles by themselves are noteffectively deposited onto skin and/or hair from rinse-off applications.

It is desirable to provide an effective level of hydrophilic skin and/orhair benefit materials. However, the deposition of hydrophilic benefitagents such as glycerine, dihydroxyacetone (DHA), and others from arinse-off application has been a tremendous challenge resulting in noconsumer benefit due to low deposition efficiency. Thus, there stillremains the need for a rinse-off product that more effectively depositsbenefit agents.

SUMMARY

The present invention relates to a personal care composition thatcomprises a hydrophilic liquid, a structurant for said hydrophilicliquid, a surface active, a lipid, and an aqueous phase, wherein saidlipid, said hydrophilic liquid, said structurant, and said surfaceactive form a lipid phase; wherein said lipid, said hydrophilic liquid,said structurant, said surface active are connected to said lipid in alipid phase. One embodiment of the present invention relates to apersonal care composition that comprises a hydrophilic liquid, astructurant for said hydrophilic liquid, a surface active, a lipid, andan aqueous phase, wherein said structurant is selected from the groupconsisting of fluid absorbent particles, inorganic particulatethickeners, and water soluble or water swellable polymers, and whereinsaid surface active is selected from the group consisting of associationstructure forming materials, dialkylquates, ester oils, silicone oils,liquid fatty alcohols and fatty acids, and microfine particles. Anotherembodiment of the present invention relates to a personal carecomposition that comprises a hydrophilic liquid, a structurant for saidhydrophilic liquid, a surface active, a lipid, and an aqueous phase,wherein said structurant and said surface active are both associationstructure forming materials. These compositions provide improved skinand/or hair moisturization, appearance, aesthetics and skin and/or hairfeel during and/or after application, and are useful in providingimproved deposition of actives to the desired area of the skin and/orhair.

DETAILED DESCRIPTION

All percentages and ratios used herein are by weight of the totalcomposition and all measurements made are at 25° C., unless otherwisedesignated.

The compositions of the present invention can comprise, consistessentially of, or consist of, the essential as well as optionalingredients and components described herein. As used herein, “consistingessentially of” means that the composition or component may includeadditional ingredients, but only if the additional ingredients do notmaterially alter the basic and novel characteristics of the claimedcompositions or methods. It should be obvious to one skilled in the artthat other common personal care materials can be incorporated withoutaltering the substance of the invention.

The term “dermatologically-acceptable”, as used herein, means that thecompositions or components thereof so described are suitable for use incontact with human skin without undue toxicity, incompatibility,instability, allergic response, and the like.

The term “rinsable composition”, as used herein, means a compositiondesigned to be rinsed off by a liquid such as water. After thecomposition is rinsed off, hydrophilic benefit agents are deposited onthe skin and/or hair.

The term “safe and effective amount”, as used herein, means an amount ofa compound, component, or composition sufficient to significantly inducea positive benefit, preferably a positive skin and/or hairmoisturization, appearance or feel benefit, including independently thebenefits disclosed herein, but low enough to avoid serious side effects,i.e., to provide a reasonable benefit to risk ratio, within the scope ofsound medical judgment.

The term “topical application”, as used herein, means to apply or spreadthe compositions of the present invention onto the surface of the skin.

The term “hydrophilic liquid”, as used herein, means that a liquidmaterial has a strong affinity to water.

The term “skin darkening”, as used herein, means to impart color to theskin using artificial means, preferably chemical means. This termincludes compositions that produce an artificial tan similar to thatgenerated by prolonged exposure to solar radiation, and also those thatimpart a slight coloration to the skin that are not readily recognizedas an artificial tan, but rather generate a subtle color on the skinthat makes the skin appear healthier.

The term “structurant for the hydrophilic liquid”, as used herein, meansa material in combination with a liquid forming a complex with aviscosity higher than the liquid or in a form of solid or semi-solid.

The term “surface active”, as used herein, means a material forming acommon boundary of a structured hydrophilic liquid and a lipid.

The term “association structure”, as used herein, means micelles,reverse micelles, lyotropic liquid crystal structures, and α-crystalinegel structures which are formed by the mixture of a surfactant or themixture of surfactants and a polar solvent or the mixture of polarsolvents at ambient temperature.

The term “liquid crystals” or “liquid crystalline”, as used herein,means an intermediate state between the solid and liquid states. It isoften called a mesomorphic state. In the literature, liquid crystalstructures are also referred to as anisotropic fluids, or in the case ofthe cubic phase, as isotropic fluids, a fourth state of matter, liquidcrystals, aggregates, or mesophases. These terms are usedinterchangeably. Liquid crystal structures or aggregates are generallydisclosed in the reference Lyotropic Liquid Crystals Stig Friberg (Ed.),American Chemical Society, Washington, D.C., 1976, pp 13-27.

The term “α-crystaline gel”, as used herein, means a crystalline stateof the surfactant with layers of hydrophilic liquid between the polargroups. The structure of the gel is of lamellar type as is the lamellarphase. The difference is that the hydrocarbon chains are in a solidstate and orientated parallel to each other in an α-crystalline mode ofpacking.

The term “connected to”, as used herein, means a material or a phase ison the surface, within the domain, or both on the surface and within thedomain of another material or a phase.

Active and other ingredients useful herein may be categorized ordescribed herein by their cosmetic and/or therapeutic benefit or theirpostulated mode of action. However, it is to be understood that theactive and other ingredients useful herein can in some instances providemore than one cosmetic and/or therapeutic benefit or operate via morethan one mode of action. Therefore, classifications herein are made forthe sake of convenience and are not intended to limit an ingredient tothe particularly stated application or applications listed.

A. Hydrophilic Liquid

A hydrophilic liquid is a liquid with a strong affinity to water. Thehydrophilic liquids include neat liquid materials, mixtures of liquidmaterials and solid materials dissolved in hydrophilic liquids. Thehydrophilic liquids and solids have a solubility of at least 1 g in 100g of water at 25° C. The personal care compositions preferably compriseno more than about 90 weight percent of the composition of thehydrophilic liquids, more preferably no more than about 70 weightpercent, more preferably no more than about 50 weight percent. Thepersonal care compositions preferably comprise at least about 0.1 weightpercent of the composition of the hydrophilic liquids, more preferablyat least about 0.2 weight percent, even more preferably at least about0.5 weight percent. The useful skin compatible hydrophilic liquids mayinclude hydrophilic materials including, but not limited to, water,humectants, sugar amines, Vitamin B families, Vitamin C families,Natural extracts, protease inhibitors, α-hydroxyaldehydes and ketones,peptides, water soluble or swellable polymers, and mixtures thereof. Theskin benefits provided by these materials include moisturization,softness, feel, shine, desquamation, barrier improvement, wrinklerepair, anti-yellowing/sallowness, anti-irritancy, soothing, darkening,lightening, hair growth reduction, hair styling and hair conditioning.

Suitable skin compatible solvents to dissolve solid hydrophilicmaterials include, but are not limited towater, alcohols (e.g. ethanol,glycerin), polyols (e.g. Polyethyleneglycol), hydrophilic oils and/ortheir mixtures.

1. Humectants

The compositions of the present invention may contain a humectant. Thehumectants herein are selected from the group consisting of water,polyhydric alcohols, amino acids, pyrrolidone carboxylic acid and salt,hydroxyl acids, urea, urea derivatives and water soluble alkoxylatednonionic polymers, and mixtures thereof.

Polyhydric alcohols useful herein include glycerin, sorbitol, propyleneglycol, butylene glycol, hexylene glycol, ethoxylated glucose,1,2-hexane diol, hexanetriol, dipropylene glycol, erythritol, trehalose,diglycerin, xylitol, maltitol, maltose, glucose, fructose, sodiumchondroitin sulfate, sodium hyaluronate, sodium adenosine phosphate,sodium lactate, pyrrolidone carbonate, glucosamine, cyclodextrin, andmixtures thereof.

Hydroxyl acids useful herein include lactic acid and glycolic acid,salicylic acid and their salts, and mixtures thereof.

Water soluble alkoxylated nonionic polymers useful herein includepolyethylene glycols and polypropylene glycols having a molecular weightof up to about 1000 such as those with CTFA names PEG-200, PEG-400,PEG-600, PEG-1000, and mixtures thereof.

2. Electrolytes

The compositions of the present invention may include a safe andeffective amount of an electrolyte. Non-limiting examples include sodiumsalts, potassium salts, calcium salts, and mixtures thereof.

3. Sugar Amines

The compositions of the present invention may include a safe andeffective amount of a sugar amine, which are also known as amino sugars.As used herein, “sugar amine” refers to an amine derivative of asix-carbon sugar. Examples of sugar amines that are useful hereininclude glucosamine, N-acetyl glucosamine, mannosamine, N-acetylmannosamine, galactosamine, and N-acetyl galactosamine.

4. Vitamin B Family

The compositions of the present invention may contain a safe andeffective amount of a compound from the Vitamin B Family. In oneembodiment, the compositions of the present invention can contain avitamin B₃ compound. Vitamin B₃ compounds are particularly useful forregulating skin condition as described in U.S. Pat. No. 5,939,082. Asused herein, “vitamin B₃ compound” means a compound having the formula:

wherein R is —CONH₂ (i.e., niacinamide), —COOH (i.e., nicotinic acid) or—CH₂OH (i.e., nicotinyl alcohol); salts, derivatives, and mixturesthereof.

The compositions of the present invention may include a safe andeffective amount of a panthenoic acid derivative, including panthenol,dexpanthenol, ethyl panthenol, and mixtures thereof. These vitamin B₅compounds provide skin soothing, moisturizing, and anti-irritatingbenefits.

The topical compositions of the present invention may comprise a safeand effective amount of one or more vitamin B₆ compounds selected fromthe group consisting of pyridoxine, esters of pyridoxine (e.g.,pyridoxine tripalmitate), amines of pyridoxine (e.g., pyridoxamine),salts of pyridoxine (e.g., pyridoxine HCl) and derivatives thereof,including pyridoxamine, pyridoxal, pyridoxal phosphate, pyridoxic acid,and mixtures thereof. Vitamin B₆ can be synthetic or natural in originand can be used as pure compounds or mixtures of compounds (e.g.,extracts from natural sources or mixtures of synthetic materials).Vitamin B₆ is generally found in many foodstuffs, especially yeast,liver and cereals. As used herein, “vitamin B₆” includes isomers andtautomers of such. Vitamin B₆ is commercially available from SigmaChemical Co.

5. Vitamin C Family

The compositions of the present invention may include a safe andeffective amount of a compound from the Vitamin C Family. Specifically,the compositions may include ascorbic acid and its salts, and ascorbicacid derivatives (e.g. magnesium ascorbyl phosphate, sodium ascorbylphosphate, ascorbyl sorbate, ascorbyl glucoside, and mixtures thereof).These anti-oxidant/radical scavengers are especially useful forproviding protection against UV radiation which can cause increasedscaling or texture changes in the stratum corneum and against otherenvironmental agents which can cause skin damage.

6. Natural Extracts

The compositions of the present invention may include a safe andeffective amount of extracts from natural products. Non-limitingexamples include mulberry extract, placental extract, soy extract, greentea extract, and chamomile extract. These extracts provide a broad rangeof skin benefits such as anti-inflammatory, skin lightening, hair growthreduction and anti-irritancy.

7. Peptides

The compositions of the present invention may contain a safe andeffective amount of a peptide, including but not limited to, di-, tri-,tetra-, penta-, hexa-peptides, and derivatives and mixtures thereof. Asused herein, “peptide” refers to peptides containing ten or fewer aminoacids and their derivatives, isomers, and complexes with other speciessuch as metal ions (e.g., copper, zinc, manganese, magnesium, and thelike). As used herein, peptide refers to both naturally occurring andsynthesized peptides. Also useful herein are naturally occurring andcommercially available compositions that contain peptides.

8. Alpha-Hydroxy Aldehydes and Ketones

The compositions of the present invention may include alpha-hydroxyaldehydes and ketones. Examples include, but are not limited to,dihydroxyacetone, glyceraldehydes, 2,3-dihydroxy-succindialdehyde,2,3-dimethoxysuccindialdehyde, erythrulose, erythrose,2-amino-3-hydroxy-succindialdehyde and3-benzylamino-3-hydroxy-succindialdehye. These compounds have a sun-lesstanning benefit when applied to skin. As used herein, the term “sun-lesstanning” is defined as color darkening to the skin using artificialmeans, preferably chemical means. This term includes compositions thatproduce an artificial tan similar to that generated by prolongedexposure to solar radiation, and also those that impart a slightcoloration to the skin that are not readily recognized as an artificialtan, but rather generate a subtle color on the skin that makes the skinappear healthier.

9. Hexamidine

The topical compositions of the present invention may comprise a safeand effective amount of one or more hexamidines and their salts.Preferably, the hexamidine is hexamidine isethfionate. As used herein“hexamidine” includes any isomers and tautomers of such. Hexamidine iscommercially available as hexamidine isethionate under the tradenameElastab® HP100 from Laboratoires Serobiologiques.

10. Dehydroacetic Acid

The compositions of this invention may comprise dehydroacetic acid orits salts, derivatives, or tautomers thereof. These compounds are usefulin (i) reducing sebum synthesis by the pilosebaceous glands, (ii)regulating the oily and/or shiny appearance of the skin, and (iii)treating acne and other related skin disorders in mammalian skin andscalp. Dermatologically acceptable salts include alkali metal salts,such as sodium and potassium; alkaline earth metal salts, such ascalcium and magnesium; non-toxic heavy metal salts; ammonium salts; andtrialkylammonium salts, such as trimethylammonium and triethylammonium,and mixtures thereof. Sodium, potassium, and ammonium salts ofdehydroacetic acid are preferred. Derivatives of dehydroacetic acidinclude, but are not limited to, any compounds wherein the CH₃ groupsare individually or in combination replaced by amides, esters, aminogroups, alkyls, and alcohol esters. Tautomers of dehydroacetic acid arethe isomers of dehydroacetic acid which can change into one another withgreat ease so that they ordinarily exist in equilibrium. Thus, tautomersof dehydroacetic acid can be described as having the chemical formulaC₈H₈O₄.

11. Water-Soluble or Water-Swellable Polymer

The polymers useful in this invention are any water-soluble orwater-swellable polymer suitable for use in personal care products andfor application to human skin and hair. The polymers may behomopolymers, copolymers or a blend of polymers or copolymers. Thepolymers can be natural, synthetic, or semi-synthetic. Polymers can bestraight chain or cross-linked. Polymers, containing either ionic andnon-ionic groups, are contemplated. Ionic polymers include, but are notlimited to, cationic, anionic, zwitterionic, and amphoteric polymers.The polymers can be synthesized from a variety of monomers containingunsaturated groups or by synthetic mechanisms that result in a varietyof linking groups, including polyurethanes, polyesters, polyamides, andpolyureas in the polymer backbone.

Examples of useful commercially available synthetic polymers are listedbelow. The names described are according to the nomenclature developedby the Cosmetic, Toiletry, and Fragrance Association, Inc. (CTFA). Infew cases, where the CTFA name is not available, the chemical name iswritten. Non-limiting examples include:vinylcaprolactam/PVP/dimethylamino-ethylmethacrylate copolymer (tradename: Gaffic, H2OLD, ISP Corp.), vinyl acetate/crotonic acid/vinylpropionate copolymer (trade name: Luviset, BASF), vinylacetate/crotonates copolymer (trade name: Resyn, National Starch Corp.),vinyl acetate/butyl maleate/isobomyl acrylate copolymer (trade name:Advantage CPV, ISP), tyrene/vinylpyrrolidone copolymer (trade name:Polectron, ISP); vinylpyrrolidone/vinyl acetate copolymers (ISP, BASF);polyvinylpyrrolidone/polyurethane interpolymer (Pecogel, Phoenix);octylacrylamide/acrylates/butylaminoethylmethacrylate copolymer(Amphomer, National Starch); quaternizedvinylpyrrolidone/dimethylaminoethyl methacrylate copolymer(Polyquaternium-11, ISP), vinylpyrrolidone/vinyl acetate/vinylpropionate copolymer (Luviskol, BASF). In addition, other commerciallyavailable polymers listed in the Encyclopedia of Polymers andThickeners, Cosmetic and Toiletries, page 95, Vol. 108, May 1993 can beincluded in this invention.

Examples of natural and modified natural polymers are: copolymer ofhydroxyethyl-cellulose and dimethyldiallyl ammonium chloride(Polyquaternium-4; National Starch), hydroxyethyl-cellulose (Natrosol;Aqualon), xanthan gum (Calgon), and other polymers listed in theEncyclopedia of Polymers and Thickeners, Cosmetic and Toiletries, page95, Vol. 108, May 1993 can be included in this invention.

Polymers that may be useful in the present invention are silicone graftcopolymers listed in the U.S. Pat. Nos. 5,565,193 and 5,622,694;hydrophobic graft copolymers are listed in U.S. Pat. No. 5,622,694;silicone block copolymers are listed in U.S. Pat. No. 6,074,628.

The water-soluble or water-swellable polymers of the present inventionmay also include carboxylic acid/carboxylate copolymers. The carboxylicacid/carboxylate copolymers herein can include cross-linked copolymersof carboxylic acid and alkyl carboxylate, and can have an amphophilicproperty. Commercially available carboxylic acid/carboxylate copolymersuseful herein include: CTFA name Acrylates/C₁₀₋₃₀ Alkyl AcrylateCrosspolymer having tradenames Pemulene TR-1, Pemulene TR-2, Carbopol1342, Carbopol 1382, and Carbopol ETD 2020, all available from B. F.Goodrich Company.

12. Colorants

The composition of the present invention may include a colorant. Ingeneral, colorants are those substances that provide color to a personalcare product. The purpose of the colorant is to deliver the desirableshade or color to skin or hair that the user is seeking as well as toeven out skin tone by covering or hiding tonal imperfections. Suchcolorants should be physically and chemically compatible with theessential components described herein, or should not otherwise undulyimpair product stability, aesthetics or performance. Useful colorantsherein include water soluble dyes. Water soluble dyes, identified by oneskilled in the art, are dyes that are substantially soluble in aqueoussolutions. Non-limiting examples of water soluble acid dyes include D&CRed 33, FD&C Yellow No. 5, D&C Green No. 5, D&C Yellow No. 8, and D&CYellow No. 10.

The composition of the present invention may include an oxidizing agent(e.g. peroxides), and/or oxidative dye precursors (including developersand/or couplers when present).

B. Structurant for the Hydrophilic Liquid

The compositions of the present invention may contain a structurant forthe hydrophilic liquid. A structurant mixed with a liquid forms acomplex with a viscosity higher than the liquid or in a form of solid orsemi-solid. The combination of the hydrophilic liquid and structurantform a material having a preferred viscosity of at least about 3000 cst(centistokes) at 25° C., preferably at least about 5000 cst. Thestructurants herein are used to immobilize hydrophilic liquids. Usefulstructurants include association structure forming materials, fluidabsorbent particles, inorganic particulate thickeners, and water-solubleor water-swellable polymers. Preferably the ratio of structurant tohydrophilic liquid is from about 1:1000 to about 100:1, more preferablyfrom about 1:200 to about 80:1, still more preferably from about 1:100to about 50:1, and even more preferably from about 1:20 to about 20:1.

1. Association Structure Forming Materials

The personal care compositions of the present invention may includeassociation structure forming materials. The association structureforming materials comprise from about 0.1% to about 80% of the personalcare composition. Preferably the association structure forming materialscomprise from about 0.2% to about 70%, of the personal care composition.

Use of the association structure forming materials in the presentinvention provides a method of encapsulating active ingredients. Theactive ingredients are encapsulated by combining a surface active(described herein) and a hydrophilic liquid (described herein) to forman association structure; dispersing the association structure in alipid phase (described herein); and dispersing the lipid phase in anaqueous phase (described herein).

The association structures of the present invention may be micelles,reverse micelles, lyotropic liquid crystals, α-crystalline gels andmixtures thereof. Reverse micelles are also known in the art asspherical reverse micelles, elongated reverse micelles, bicontinuousphase or L2 phase; cylindrical reverse micelles or reverse connectedrod-shaped liquid crystals also known in the art as networking reversecylinders, connected cylindrical reverse micelle structures, orconnected cylinders. Lyotropic Liquid Crystals include: 1) reversehexagonal liquid crystals, also known in the art as hexognal II or Fphase; 2) cubic liquid crystals, also known in the art as viscousisotropic and I₂ phase; 3) lamellar liquid crystals, also known in theart as the Lα neat phase and D phase; and 4) cholesteric liquidcrystals, an anisotropic subclass of polymeric lyotropic liquid crystal.The centers of gravity of the polymeric particles are arranged at randomwith no positional order, but only an orientational order exists.

Preferred association structures are the cylindrical reverse micelle,reverse hexagonal liquid crystals, cubic liquid crystals, lamellarliquid crystals, cholesteric liquid crystals, and mixtures thereof. Theassociation structures can be in the following phases: two phase liquidcrystals, one phase liquid crystals, reverse micelles/liquid crystallinephase or liquid crystalline/solvent phase.

Any surfactant and/or polymers which forms association structures atambient temperature and is suitable for use in personal carecompositions, is suitable for use herein. Surfactants suitable for usein personal care compositions do not present dermatological ortoxicological problems. Anionic surfactants, nonionic surfactants,cationic surfactants, amphoteric surfactants and mixtures thereof aresuitable for use.

Types of anionic surfactants suitable for use are soaps; sulfonates suchas alkane sulfonates (e.g., branched sodium x-alkane sulfonate wherex≠1) paraffin sulfonates, alkylbenzene sulfonates, a-olefin sulfonates,sulfosuccinates and sulfosuccinate esters (e.g., dioctylsodium anddisodium laureth sulfosuccinate), oisethionates, acylisethionates (e.g.,sodium 2-lauroyloxyethane sulfonate), and sulfalkylamides of fattyacids, particularly N-acylmethyltaurides; sulfates such as alkylsulfates, ethoxylated alkyl sulfates, sulfated monoglycerides, sulfatedmonoglycerides, sulfated alkanolamides, and sulfated oils and fats;carboxylates such as alkyl caboxylate having a carbon chain length aboveC₁₂, acylsarcosinates, sarcosinates (e.g., sodium lauryl sarcosinate),ethoxylated carboxylic acid sodium salts, carboxylic acids and salts(e.g., potassium oleate and potassium laurate), ether carboxylic acids;ethoxylated carboxylic acids and salts (e.g., sodium carboxymethyl alkylethoxylate; phosphoric acid esters and salts (e.g., lecithin);acylglutamates (e.g., disodium n-lauroyl glutamate) and mixturesthereof. It should be noted that the safest alkyl sulfates for usegenerally have a hydrocarbon chain lengths above C₁₂.

Types of nonionic surfactants suitable for use are polyoxyethylenes suchas ethoxylated fatty alcohols, ethoxylated alcohols (e.g.,octaoxyethelene glycol mono hexadecyl ether, C₁₆E₈ and C₁₂E₈),ethoxylated fatty acids, ethoxylated fatty amines, ethoxylated fattyamides, ethoxylated alkanolamides, ethoxylated alkyl phenol, andethoxylated sterols; triesters of phosphoric acid (e.g., sodiumdioleylphosphate); alkyl amido diethylamines; alkylamido propylbetaines(e.g., cocoamido propylbetaine); amine oxide derivatives such alkyldimethylamine oxides, alkyl dihydroxyethylamine oxides, alkylamidodimethylamine oxidesand alkyl amidodihydroxyethylamine oxides;polyhydroxy derivatives such as polyhydric alcohol esters and ethers(e.g., sucrose monooleate, cetostearyl glucoside, β octylglucofuranoside, esters, alkyl glucosides having a carbon chain lengthof from C₁₀ to C₁₆), mono, di- and polyglycerol ethers and polyglycerolesters (e.g., tetraglycerol monolaurate and monoglycerides, triglycerolmonooleate (such as TS-T122 supplied by Grinsted), diglycerol monooleate(such as TST-T101 supplied by Grinsted), ethoxylated glycerides;monoglycerides such as monoolein, monolaurin and monlinolein;diglyceride fatty acids such as diglycerol monoisostearate (e.g., Cosmol41 fractionated supplied by Nisshin oil Mills, Ltd.) and mixturesthereof.

Types of cationic surfactants suitable for use are aliphatic-aromaticquaternary ammonium halides; quaternary ammonium alkyl amidoderivatives; alkyl amidopropyldimethylammonium lactate;alkylamidopropyldihydroxyethylammo-nium lactate; alkyl amidopropylmorpholinium lactate; quaternary ammonium lanolin salts; alkylpyridinium halides; alkyl isoquinolinium halides; alkyl isoquinoliniumhalides; quaternary ammonium imidazolinium halides; bisquaternaryammonium derivatives; alkylbenzyl dimethylammonium salts such asstearalkylammonium chloride; alkylbetaines such asdodecyldimethylammonium acetate and oleylbetaine; alkylethylmorpholiniumethosulfaates; tetra alkyl ammonium salts such as dimethyl distearylquaternary ammonium chloride and bis isostearamideopropyl hydroxypropyldiammonium chloride (Schercoquat 2IAP from Scher Chemicals);heterocyclic ammonium salts; bis(triacetylammoniumacetyl)diamines andmixtures thereof.

Types of amphoteric surfactants suitable for use are alkyl betaines;alkanolamides such as monoalkanolamides and dialkanolamides; alkyl amidopropylbetaines; alkyl amidopropylhydroxysultaines; acylmonocarboxyhydroxyethyl glycinates; acyldicarboxy hydroxyethyl glycinates; alkylaminopropionates such as sodium laurimino dipropionate; alkyliminodipropionates; amine oxides; acyl ethylenediamine betaines;N-alkylamino acids such as sodium N-alkylamino acetate;N-lauroylglutamic acid cholesterol esters; alkyl imidazolines andmixtures thereof. Association structure forming materials may includepolymers such as alkoxylated polymers and polysaccharides. The polymersmay have a molecular weight of from about 500 to about 1,000,000. Lowermolecular weight polymers within the range of from about 750 to about500,000 are preferred, and those with molecular weights of from about1,000 to about 60,000 are even more preferred. Polysaccharides useful inthe present invention include polyglucose materials, gums,hydrocolloids, cellulose and cellulose-derivative polymers. Many ofthese and other suitable polysaccharides are described in IndustrialGums—Polysaccharides and Their Derivatives, Roy L. Whistler, AcademicPress (New York), 1959 and also in P. Weigel et al., “Liquid CrystallineStates in Solutions of Cellulose and Cellulose Derivatives,” ActaPolymerica Vol. 35 No. 1, 1984, pp. 83-88. Useful polysaccharidesinclude nonionic, anionic and cationic polysaccharides. Preferrednonionics include the hydroxypropyl cellulose polymers known as theKLUCEL series available from Hercules, Inc. and xantham guy availablefrom Kelco. Preferred anionic polymers are the sodium alginates(available from Kelco) and sodium carboxymethylcellulose polymeravailable from Hercules. Preferred cationic polymers are CHITOSAN andCHITIN from Protan, Inc, and also depolymerised guar, such as T4406 fromHi Tek Polymers. Alkoxylated polymers useful in the present inventioninclude the Poloxamer Series of EO-PO condensates (A-B-A type blockcopolymers of polyoxyethylene and polyoxypropylene). Suitable examplesof polyoxyethylene-polyoxypropylene block copolymers include Poloxamers403, 402, and 401 available under the tradenames PLURONIC P123, PLURONICL-122, and PLURONIC L-121 from BASF and Hodag Nonionic 1123-P and HodanNonionc 1122-L from Calgene and SYNPERONIC PE/L121 from ICI.

Also useful herein are silicone copolyols and aminosilicones. Suitableexamples include DC-190, DC-193, DC5329, Q4-3667 from Dow Corning;Silwet L-7622 and Silwet L-77 from Union Carbide.

2. Fluid Absorbent Particles

The compositions of the present invention may comprise fluid-absorbentparticles. The fluid-absorbent particles can be any material thatremains solid within the composition, including porous, hydrophilic, andsolid particles. The fluid absorbent particles may have an averageparticle size of from about 0.001 microns to about 2000 microns,preferably from about 0.01 microns to about 200 microns, more preferablyfrom about 0.1 microns to about 100 microns. The fluid-absorbentparticles for use in the compositions of the present invention includemoisture-absorbent materials such as silicas (or silicon dioxides),silicates, carbonates, various organic copolymers, and combinationsthereof. The silicates are most typically those formed by reaction of acarbonate or silcate with an alkali metal, alkaline earth metal, ortransition metal, specific non-limiting examples of which includecalcium silicate, amorphous silicas (e.g., precipitated, fumed, andcolloidal), calcium carbonate (e.g., chalk), magnesium carbonate, zinccarbonate, and combinations thereof. Non-limiting examples of somesuitable silicates and carbonates for use herein are described in VanNostrand Reinhold's Encyclopedia of Chemistry, 4^(th) edition, pages155, 169, 556, and 849 (1984). Absorbent powders are also described inU.S. Pat. No. 6,004,584.

Other fluid-absorbent particles suitable for use herein include kaolin,(hydrated aluminum silicates), mica, talc (hydrated magnesiumsilicates), starch or modified starch, microcrystalline cellulose (e.g.,Avicel from FMC Corporation), or other functionally similarfluid-absorbent polymer, any other silica-containing ornon-silica-containing powder.

Other fluid-absorbent particles suitable for the use herein includesuper-absorbent polymers. By definition, a superabsorbent polymer mustabsorb a minimum of 20 times its own weight in water. Moreover, thepolymer must retain its original identity and have sufficient physicalintegrity to resist flow and fusion with neighboring particles, and toswell to equilibrium volume and not dissolve. Non-limiting examplesinclude Water Lock® superabsorbent polymers (e.g. Starch graft poly(2-propenamide-co-2-propenoic acid) sodium or potassium salt,2-propenamide-co-2-propenoic acid copolymer, sodium salt) manufacturedby Grain Processing Corporation.

3. Inorganic Particulate Thickeners

The compositions of the invention may also include inorganic particulatethickener. These inorganic particles form a stable network withhydrophilic liquids. Non-limiting examples include silica and clay (e.g.Benton clays from Rhox) with particle size less than 1 micrometer.

4. Water-Soluble or Water-Swellable Polymers

Description is same as above in the hydrophilic liquid section.

C. Surface Active

The compositions of the present invention include surface actives. Thesurface actives form a common boundary of a structured hydrophilicliquid and a lipid. The surface actives contain polar groups andnon-polar groups. This property can be measured by a contact anglemethod. The contact angles of the surface actives on both a hydrophobicsurface (polyethylene terephthalate) and a hydrophilic surface (aluminumfoil) are no more than 60°, preferably no more than 50°, and even morepreferably no more than 40° for materials which can be applied to thesurfaces as drops. Contact angles of diiodomethane and water on thinfilms of surface actives that are too thick to form drops on the solventsurfaces are no more than 90°, preferably no more than 80°, even morepreferably no more than 70°. Preferably the solubility parameter ofsurface actives is at least 3 units different from that of thehydrophilic liquid, more preferably at least 4 units different, stillmore preferably at least 5 units from that of the hydrophilic liquid.Preferably the solubility parameter of the surface actives is at least 1unit different from that of the lipid described herein, more preferablyat least 1.5 units different and even more preferably at least 2 unitsdifferent from that of the lipid. The ratio of surface active tohydrophilic liquid is from about 1:1000 to about 20:1, more preferablyfrom about 1:100 to about 15:1, still more preferably from about 1:10 toabout 10:1.

The surface actives can be combined with the structured hydrophilicliquids during formulating the product. Alternatively, the structuredhydrophilic liquids can be treated with the surface actives by a surfacetreatment house (e.g. KOBO products, US Cosmetics).

1. Association Structure Forming Materials

In one embodiment of the present invention, both the structurant for thehydrophilic liquid and the surface active are association structureforming materials. The description is the same as above in thestructurant for the hydrophilic liquid section.

2. Film Forming Materials

In one embodiment of the present invention, the structurant for thehydrophilic liquid and the surface active are not both associationstructure forming materials. In this embodiment, the surface active maybe film forming materials selected from dialkylquates, ester oils,silicone oils and waxes, liquid fatty alcohols and fatty acids, andmicrofine particles.

a. Dialkylquates

The present compositions may include a dialkylquaternary compound.Non-limiting examples include dialkyl dimethyl quaternaries (e.g.dialkyl(C₁₂-C₁₈)dimethyl ammonium chloride, ditallow dimethyl ammoniumchloride, distearyl dimethyl ammonium methyl sulfate) and imidazoliniumquaternaries (e.g. methyl-1-oleyl amido ethyl-2-oleylimidazolinium-methyl sulfate).

b. Ester Oils

Ester oils have at least one ester group in the molecule. One type ofcommon ester oil useful in the present invention are the fatty acid monoand polyesters such as cetyl octanoate, octyl isonanoanate, myristyllactate, cetyl lactate, isopropyl myristate, myristyl myristate,isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate,cholesterol isostearate, glycerol monostearate, glycerol distearate,glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate;sucrose ester and polyesters, sorbitol ester, and the like. A secondtype of useful ester oil is predominantly comprised of triglycerides andmodified triglycerides. These include vegetable oils such as jojoba,soybean, canola, sunflower, safflower, rice bran, avocado, almond,olive, sesame, persic, castor, coconut, and mink oils. Synthetictriglycerides can also be employed provided they are liquid at roomtemperature. Modified triglycerides include materials such asethoxylated and maleated triglyceride derivatives provided they areliquids. Proprietary ester blends such as those sold by Finetex asFinsolv are also suitable, as is ethylhexanoic acid glyceride. A thirdtype of ester oil is liquid polyester formed from the reaction of adicarboxylic acid and a diol. Examples of polyesters suitable for thepresent invention are the polyesters marketed by ExxonMobil under thetrade name PURESYN ESTER.RTM.

c. Silicone Oils and Waxes

The compositions of the present invention may include silicone oils andwaxes. Silicone oils and waxes include polydimethyl siloxane, organofunctional silicones (alkyl and alkyl aryl, copolyol), and aminosilicones.

d. Liquid Fatty Alcohols and Fatty Acids

The liquid fatty alcohols useful herein include those having from about10 to about 30 carbon atoms. These liquid fatty alcohols may be straightor branched chain alcohols and may be saturated or unsaturated alcohols.Liquid fatty alcohols are those fatty alcohols which are liquid at 25°C. Nonlimiting examples of these compounds include oleyl alcohol,palmitoleic alcohol, isostearyl alcohol, isocetyl alcohol, and mixturesthereof. While poly fatty alcohols are useful herein, mono fattyalcohols are preferred.

The fatty acids useful herein include those having from about 10 toabout 30 carbon atoms. These fatty acids can be straight or branchedchain acids and can be saturated or unsaturated. Suitable fatty acidsinclude, for example, oleic acid, linoleic acid, isostearic acid,linolenic acid, ethyl linolenic acid, arachidonic acid, ricinolic acid,and mixtures thereof.

e. Microfine Particles

The present compositions may include microfine particles as surfaceactives. The microfine particles are dispersible both in water and inoil. The average diameter of the particles used is from about 1 nm toabout 200 nm. Advantageous particles are all those which are suitablefor stabilizing water-in-oil Pickering emulsions. The amphiphiliccharacteristics can also be achieved with the surface treatments ofthese microfine particles. Non-limiting examples of microfine particlesinclude metal oxides and boron nitrides. Non-limiting surface coatingsinclude silicones, silicone derivatives silca, gel, aluminium hydroxide,and alumina.

D. Lipid/Lipid Phase

The composition of the present invention may include a skin compatiblelipid. A skin compatible lipid is defined herein, as a lipid that isliquid, semi-solid, or solid at the temperature at which bathing iscarried out that is deemed safe for use in cosmetics being either inertto the skin or actually beneficial. Lipids useful herein may includeoils and waxes. Useful skin compatible lipids for the present inventioninclude ester lipids, hydrocarbon lipids, and silicone lipids.

Ester lipids have at least one ester group in the molecule. One type ofcommon ester lipids useful in the present invention are the fatty acidmono and polyesters such as cetyl octanoate, octyl isonanoanate,myristyl lactate, cetyl lactate, isopropyl myristate, myristylmyristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyloleate, cholesterol isostearate, glycerol monostearate, glyceroldistearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyltartrate, sucrose ester and polyesters, sorbitol ester, and the like.

A second type of useful ester lipids is predominantly comprised oftriglycerides and modified triglycerides. These include vegetable oilssuch as jojoba, soybean, canola, sunflower, safflower, rice bran,avocado, almond, olive, sesame, persic, castor, coconut, and mink oils.Synthetic triglycerides can also be employed provided they are liquid atroom temperature. Modified triglycerides include materials such asethoxylated and maleated triglyceride derivatives provided they areliquids. Proprietary ester blends such as those sold by Finetex asFinsolv are also suitable, as is ethylhexanoic acid glyceride.

A third type of ester lipids is liquid polyester formed from thereaction of a dicarboxylic acid and a diol. Examples of polyesterssuitable for the present invention are the polyesters marketed byExxonMobil under the trade name PURESYN ESTER.RTM.

A second class of skin compatible lipids suitable for the presentinvention is liquid and semi-solid hydrocarbons. These include linearand branched oils such as liquid paraffin, squalene, squalane, mineraloil, low viscosity synthetic hydrocarbons such as polyalphaolefin soldby ExxonMobil under the trade name of PURESYN PAO and polybutene underthe trade name PANALANE or INDOPOL. Light (low viscosity), highlybranched hydrocarbon oils are also suitable.

Petrolatum is a hydrocarbon material and a useful component of thepresent invention. Its semi-solid nature can be controlled both inproduction and by the formulator through blending with other oils.

A third class of useful skin compatible lipids is silicone based. Theyinclude linear and cyclic polydimethyl siloxane, organo functionalsilicones (alkyl and alkyl aryl), and amino silicones.

A fourth class of useful skin compatible lipids is liquid fattyalcohols. Useful liquid fatty alcohols herein include those having fromabout 10 to about 30 carbon atoms. These liquid fatty alcohols may bestraight or branched chain alcohols and may be saturated or unsaturatedalcohols. Liquid fatty alcohols are those fatty alcohols which areliquid at 25° C. Nonlimiting examples of these compounds include oleylalcohol, palmitoleic alcohol, isostearyl alcohol, isocetyl alcohol, andmixtures thereof. While poly fatty alcohols are useful herein, monofatty alcohols are preferred.

A fifth class of useful skin compatible lipids is liquid fatty acids.The liquid fatty acids useful herein include those having from about 10to about 30 carbon atoms. These fatty acids can be straight or branchedchain acids and can be saturated or unsaturated. Suitable fatty acidsinclude, for example, oleic acid, linoleic acid, isostearic acid,linolenic acid, ethyl linolenic acid, arachidonic acid, ricinolic acid,and mixtures thereof.

The lipids of the present invention may be part of a lipid phase. Thelipid phase is comprised of three components: a skin compatible lipid, acomplex containing a hydrophilic liquid and a structurant, and a surfaceactive. The complex containing a hydrophilic liquid and a structurant iswrapped with the surface active and mixed with the lipid, forming alipid phase. The hydrophilic liquid, the structurant, and the surfaceactive may be on the surface of the lipid, within the domain of thelipid, or both on the surface and within the domain of the lipid in thelipid phase. The lipid phase is then mixed with the aqueous phase. Thelipid phase may be either dispersed in the aqueous phase, connected tothe aqueous phase, or both dispersed and connected to the aqueous phase.

To ensure effective deposition and retention to the skin, the lipidphase or structured lipid phase should have a viscosity in the range offrom about 100 to about 200,000 poise measured at 1 Sec⁻¹, preferablyfrom about 200 to about 100,000 poise, and even more preferably fromabout 200 to about 50,000 poise as determined using the Lipid RheologyMethod described herein.

As the lipid phase may be connected to the aqueous phase, the lipidphase will have negligible solubility in the aqueous phase. The shearindex is a measure of how shear thinning the materials are as describedin the Lipid Rheology Method described herein. It is preferred that theskin compatible lipid be shear thinning either by virtue of itscomposition or the structurants that may be added. Preferably, the shearindex of the dispersed lipid phase will be less than about 0.9, morepreferably less than about 0.75, even more preferably less than about0.6, even more preferably less than about 0.45, and still morepreferably less than about 0.3.

The lipid phase preferably comprises no more than about 95 weightpercent of the lipid, preferably no more than about 90 weight percent,and more preferably no more than about 85 weight percent of the lipid.The lipid phase preferably comprises at least about 1 weight percent,more preferably at least about 5 weight percent, and still morepreferably at least about 10 weight percent of the lipid.

The composition preferably comprises no more than about 95 weightpercent of the lipid phase, preferably no more than about 90 weightpercent, and more preferably no more than about 85 weight percent of thelipid phase. The composition preferably comprises at least about 1weight percent, more preferably at least about 5 weight percent, andstill more preferably at least about 10 weight percent of the lipidphase.

The lipid phase may also contain oil-soluble or dispersible skin benefitmaterials. Non-limiting examples include oil-soluble sun screens,particles (e.g. silica, talc), surface modified particles, pigments(e.g. metal oxides, interference pigment, metallic pigment), oil-solubledyes, and perfumes.

E. Aqueous Phase

The compositions of the present invention may include an aqueous phase.The aqueous phase of the present invention preferably comprises no morethan about 90 weight percent of a fluid, more preferably no more thanabout 85%, even more preferably no more than about 80%. The aqueousphase of the present invention preferably comprises at least about 10weight percent of a fluid, more preferably at least about 15%, even morepreferably at least about 20%. The term “fluid” as used herein meanswater, mono- and polyhydric alcohols (glycerin, propylene glycol,ethanol, isopropanol, etc.), or any liquid material which is watermiscible. The lipid phase described above may be on the surface and/orwithin the domain of said aqueous phase. Also, the lipid phase may beone visually distinct phase that is packaged in physical contact withthe aqueous phase while maintaining stability.

In one embodiment, there composition may not comprise an aqueous phase.In absence of the aqueous phase, the product forms include, but are notlimited to, lipid based liquids and/or solid bars.

The compositions of the present invention may include one or morestructurants in the aqueous phase. The structurant may act as athickener to increase the viscosity of the aqueous phase. Thestructurant may also form vesicles or other structures to form domainsof water in the aqueous phase. The advantage of using an aqueous phasestructurant is to further decrease the mobility of water, and as aresult, lower the tendency of hydrophilic actives to quickly partitioninto the aqueous phase. Because different structurants may interact withthe aqueous phase with different efficiencies, it is difficult toprovide an accurate compositional range. However, when present, thecomposition preferably comprises no more than about 20 weight percent,more preferably no more than about 15 weight percent, and still morepreferably no more than about 10 weight percent of the personal carecomposition. When present, the aqueous phase structurant preferablycomprises at least about 0.01 weight percent, more preferably at leastabout 0.05 weight percent, and still more preferably at least about 0.1weight percent of the personal care composition.

Non-limiting examples of inorganic water structurants for use in thepersonal care composition include silicas, clays such as a syntheticsilicates (Laponite XLG and Laponite XLS from Southern Clay), ormixtures thereof.

Non-limiting examples of charged polymeric water structurants for use inthe personal care composition include Acrylates/Vinyl IsodecanoateCrosspolymer (Stabylen 30 from 3V), Acrylates/C10-30 Alkyl AcrylateCrosspolymer (Pemulen TR1 and TR2), Carbomers, AmmoniumAcryloyldimethyltaurate/VP Copolymer (Aristoflex AVC from Clariant),Ammonium Acryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer(Aristoflex HMB from Clariant), Acrylates/Ceteth-20 Itaconate Copolymer(Structure 3001 from National Starch), Polyacrylamide (Sepigel 305 fromSEPPIC), or mixtures thereof.

Non-limiting examples of water soluble polymeric structurants for use inthe personal care composition include cellulosic gel, hydroxypropylstarch phosphate (Structured XL from National Starch), polyvinylalcohol, or mixtures thereof.

Nonlimiting examples of associative water structurants for use in thepersonal care composition include xanthum gum, gellum gum, pectin,alginate, or mixtures thereof.

Nonlimiting examples of associative water structurants for use in thepersonal care composition include phospholipids (e.g. lecithin),dialkylquats and other association structure forming materials describedabove in the structurant for the hydrophilic liquid section.

F. Optional Ingredients

The compositions of the present invention may contain one or moreadditional skin care components in either the aqueous phase or the lipidphase. In a preferred embodiment, where the composition is to be incontact with human keratinous tissue, the additional components shouldbe suitable for application to keratinous tissue, that is, whenincorporated into the composition they are suitable for use in contactwith human keratinous tissue without undue toxicity, incompatibility,instability, allergic response, and the like within the scope of soundmedical judgment.

The CTFA Cosmetic Ingredient Handbook, Second Edition (1992) describes awide variety of nonlimiting cosmetic and pharmaceutical ingredientscommonly used in the personal care industry, which are suitable for usein the compositions of the present invention.

In any embodiment of the present invention, however, the additionalcomponents useful herein can be categorized by the benefit they provideor by their postulated mode of action. However, it is to be understoodthat the additional components useful herein can in some instancesprovide more than one benefit or operate via more than one mode ofaction. Therefore, classifications herein are made for the sake ofconvenience and are not intended to limit the active to that particularapplication or applications listed.

1. Structurant for Lipid and/or Lipid Phase

The present invention may optionally comprise a lipid structurant. Thestructurant can provide the dispersed phase with the correct Theologicalproperties. This can aid in providing effective deposition and retentionto the skin. The structured lipid phase should have a viscosity in therange of from about 100 to about 200,000 poise measured at 1 Sec⁻¹,preferably from about 200 to about 100,000 poise, and even morepreferably from about 200 to about 50,000 poise, as determined using theLipid Rheology Method described below. The amount of structurantrequired to produce this viscosity will vary depending on the oil andthe structurant, but in general, the structurant will preferably be lessthan 75 weight percent of the dispersed lipid phase, more preferablyless than 50 weight percent, and still more preferably less than 35weight percent of the dispersed lipid phase.

The structurant can be either an organic or inorganic structurant.Examples of organic thickeners suitable for the invention include solidfatty acid esters, natural or modified fats, fatty acid, fatty amine,fatty alcohol, natural and synthetic waxes, and petrolatum, and theblock copolymers sold under the name KRATON by Shell. Inorganicstructuring agents include hydrophobically modified silica orhydrophobically modified clay. Nonlimiting examples of inorganicstructurants include BENTONE 27V, BENTONE 38V or BENTONE GEL MIO V fromRheox; and CAB-O-SIL TS720 or CAB-O-SIL M5 from Cabot Corporation.

Structurants meeting the above requirements with the selected skincompatible oil can form a 3-dimensional network to build up theviscosity of the selected oils. It has been found that such structuredlipid phases, i.e., built with the 3-dimensional network, are extremelydesirable for use as wet-skin treatment compositions used in bathing.These structured oils can deposit and be retained very effectively onwet skin and retained after rinsing and drying to provide long-lastingafter wash skin benefit without causing a too oily/greasy wet and dryfeel. It is believed that the highly desirable in-use and after-useproperties of such structured oils are due to their shear thinningrheological properties and the weak structure of the network. Due to itshigh low-shear viscosity, the 3-dimensional network structured oil canstick and retain well on the skin during application of the skinconditioner. After being deposited on the skin, the network yieldseasily during rubbing due to the weak structuring of the crystal networkand its lower high-shear viscosity.

2. Surfactants

A wide variety of surfactants can be useful herein, both foremulsification of the dispersed phase as well as to provide acceptablespreading and in use properties for non-lathering systems. For cleansingapplications, the surfactant phase also serves to clean the skin andprovide an acceptable amount of lather for the user. The compositionpreferably contains no more than about 50 weight percent of asurfactant, more preferably no more than about 30 weight percent, stillmore preferably no more than about 15 weight percent, and even morepreferably no more than about 5 weight percent of a surfactant. Thecomposition preferably contains at least about 0.1 weight percent of asurfactant, more preferably at least about 1 weight percent, still morepreferably at least about 3 weight percent, and even more preferably atleast about 5 weight percent of a surfactant. For cleansing applicationsthe personal care compositions preferably produces a Total Lather Volumeof at least 300 ml, more preferably greater than 600 ml as described inthe Lathering Volume Test. The personal care compositions preferablyproduces a Flash Lather Volume of at least 100 ml, preferably greaterthan 200 ml, more preferably greater than 300 ml as described in theLathering Volume Test.

In one embodiment, the composition comprises an additional aqueous phasethat is a visually distinct phase that is packaged in physical contactwith the composition while maintaining stability. The additional aqueousphase may comprise a surfactant. In this embodiment, the hydrophilicliquid, structurant, surface active, and lipid phase may be within thedomain of one aqueous phase, while the additional aqueous phasecomprises a surfactant. The two aqueous phases (one with the surfactantand one with the hydrophilic liquid, structurant, surface active, andlipid phase) may be visually distinct phases that are packaged inphysical contact and maintain stability.

Preferable surfactants include those selected from the group consistingof anionic surfactants, nonionic surfactants, amphoteric surfactants,non-lathering surfactants, emulsifiers and mixtures thereof.Non-limiting examples of surfactants useful in the compositions of thepresent invention are disclosed in U.S. Pat. No. 6,280,757.

a. Anionic Surfactants

Non-limiting examples of anionic surfactants useful in the compositionsof the present invention are disclosed in McCutcheon's, Detergents andEmulsifiers, North American edition (1986), published by alluredPublishing Corporation; McCutcheon's, Functional Materials, NorthAmerican Edition (1992); and U.S. Pat. No. 3,929,678, to Laughlin etal., issued Dec. 30, 1975.

A wide variety of anionic surfactants are useful herein. Non-limitingexamples of anionic surfactants include those selected from the groupconsisting of sarcosinates, sulfates, isethionates, taurates,phosphates, lactylates, glutamates, and mixtures thereof. Amongst theisethionates, the alkoyl isethionates are preferred, and amongst thesulfates, the alkyl and alkyl ether sulfates are preferred.

Other anionic materials useful herein are fatty acid soaps (i.e., alkalimetal salts, e.g., sodium or potassium salts) typically from a fattyacid having from about about 8 to about 24 carbon atoms, preferably fromabout 10 to about 20 carbon atoms. These fatty acids used in making thesoaps can be obtained from natural sources such as, for instance, plantor animal-derived glycerides (e.g., palm oil, coconut oil, soybean oil,castor oil, tallow, lard, etc.) The fatty acids can also besynthetically prepared. Soaps and their preparation are described indetail in U.S. Pat. No. 4,557,853.

Other anionic materials include phosphates such as monoalkyl, dialkyl,and trialkylphosphate salts. Non-limiting examples of preferred anioniclathering surfactants useful herein include those selected from thegroup consisting of sodium lauryl sulfate, ammonium lauryl sulfate,ammonium laureth sulfate, sodium laureth sulfate, sodium tridecethsulfate, ammonium cetyl sulfate, sodium cetyl sulfate, ammonium cocoylisethionate, sodium lauroyl isethionate, sodium lauroyl lactylate,triethanolamine lauroyl lactylate, sodium caproyl lactylate, sodiumlauroyl sarcosinate, sodium myristoyl sarcosinate, sodium cocoylsarcosinate, sodium lauroyl methyl taurate, sodium cocoyl methyltaurate, sodium lauroyl glutamate, sodium myristoyl glutamate, andsodium cocoyl glutamate and mixtures thereof.

Especially preferred for use herein are ammonium lauryl sulfate,ammonium laureth sulfate, sodium lauroyl sarcosinate, sodium cocoylsarcosinate, sodium myristoyl sarcosinate, sodium lauroyl lactylate, andtriethanolamine lauroyl lactylate.

b. Non-Ionic Surfactants

Non-limiting examples of nonionic surfactants for use in thecompositions of the present invention are disclosed in McCutcheon's,Detergents and Emulsifiers, North American edition (1986), published byallured Publishing Corporation; and McCutcheon's, Functional Materials,North American Edition (1992).

Nonionic surfactants useful herein include those selected from the groupconsisting of alkyl glucosides, alkyl polyglucosides, polyhydroxy fattyacid amides, alkoxylated fatty acid esters, sucrose esters, amineoxides, and mixtures thereof.

Non-limiting examples of preferred nonionic surfactants for use hereinare those selected from the group consisting of C₈-C₁₄ glucose amides,C₈-C₁₄ alkyl polyglucosides, sucrose cocoate, sucrose laurate, lauramineoxide, cocoamine oxide and mixtures thereof.

c. Amphoteric Surfactants

The term “amphoteric surfactant,” as used herein, is also intended toencompass zwitterionic surfactants, which are well known to formulatorsskilled in the art as a subset of amphoteric surfactants.

A wide variety of amphoteric lathering surfactants can be used in thecompositions of the present invention. Particularly useful are thosewhich are broadly described as derivatives of aliphatic secondary andtertiary amines, preferably wherein the nitrogen is in a cationic state,in which the aliphatic radicals can be straight or branched chain andwherein one of the radicals contains an ionizable water solubilizinggroup, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Non-limiting examples of amphoteric surfactants useful in thecompositions of the present invention are disclosed in McCutcheon's,Detergents and Emulsifiers, North American edition (1986), published byallured Publishing Corporation; and McCutcheon's, Functional Materials,North American Edition (1992).

Non-limiting examples of zwitterionic surfactants include those selectedfrom the group consisting of betaines, sultaines, hydroxysultaines,alkyliminoacetates, imninodialkanoates, aminoalkanoates, and mixturesthereof.

Preferred surfactants for use herein include the following, wherein theanionic surfactant is selected from the group consisting of ammoniumlauroyl sarcosinate, sodium trideceth sulfate, sodium lauroylsarcosinate, ammonium laureth sulfate, sodium laureth sulfate, ammoniumlauryl sulfate, sodium lauryl sulfate, ammonium cocoyl isethionate,sodium cocoyl isethionate, sodium lauroyl isetlionate, sodium cetylsulfate, sodium lauroyl lactylate, triethanolamine lauroyl lactylate,and mixtures thereof, wherein the non-ionic surfactant is selected fromthe group consisting of lauramine oxide, cocoamine oxide, decylpolyglucose, lauryl polyglucose, sucrose cocoate, C₁₂₋₁₄ glucosamides,sucrose laurate, and mixtures thereof; and wherein the amphotericsurfactant is selected from the group consisting of disodiumlauroamphodiacetate, sodium lauroamphoacetate, cetyl dimethyl betaine,cocoamidopropyl betaine, cocoamidopropyl hydroxy sultaine, and mixturesthereof.

d. Non-Lathering Surfactants

A wide variety of non-lathering surfactants are useful herein. Thecomposition of the present invention can comprise a sufficient amount ofone or more non-lathering surfactants to emulsify the dispersed phase toyield an appropriate particle size and good application properties onwet skin.

Nonlimiting examples of these non-lathering compositions are:polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20),polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cetylphosphate, potassium cetyl phosphate, diethanolamine cetyl phosphate,Polysorbate 60, glyceryl stearate, PEG-100 stearate, polyoxyethylene 20sorbitan trioleate (Polysorbate 85), sorbitan monolaurate,polyoxyethylene 4 lauryl ether sodium stearate, polyglyceryl-4isostearate, hexyl laurate, steareth-20, ceteareth-20, PPG-2 methylglucose ether distearate, ceteth-10, diethanolamine cetyl phosphate,glyceryl stearate, PEG-100 stearate, and mixtures thereof.

e. Emulsifier Systems

In addition, there are several emulsifier mixtures that are useful insome embodiments. Examples include PROLIPID 141 (glyceryl stearate,behenyl alcohol, palmitic acid, stearic acid, lecithin, lauryl alcohol,myristyl alcohol and cetyl alcohol) and 151 (Glyceryl stearate, cetearylalcohol, stearic acid, 1-propanamium,3-amino-N-(2-(hydroxyethyl)-N-N-Dimethyl,N-C(16-18) Acyl Derivatives,Chlorides) from ISP; POLAWAX NF (Emulsifying wax NF), and INCROQUATBEHENYL TMS (behentrimonium sulfate and cetearyl alcohol) from Croda;and EMULLIUM DELTA (cetyl alcohol, glyceryl stearate, peg-75 stearate,ceteth-20 and steareth-20) from Gattefosse.

3. Cationic Polymers

The present invention may also contain organic cationic depositionpolymer Concentrations of the cationic deposition polymer preferablyrange from about 0.025% to about 3%, more preferably from about 0.05% toabout 2%, even more preferably from about 0.1% to about 1%, by weight ofthe personal care composition.

Suitable cationic deposition polymers for use in the present inventioncontain cationic nitrogen-containing moieties such as quaternaryammonium or cationic protonated amino moieties. The cationic protonatedamines can be primary, secondary, or tertiary amines (preferablysecondary or tertiary) depending upon the particular species and theselected pH of the personal cleansing composition. The average molecularweight of the cationic deposition polymer is between about 5,000 toabout 10 million, preferably at least about 100,000, more preferably atleast about 200,000, but preferably not more than about 2 million, morepreferably not more than about 1.5 million. The polymers also have acationic charge density ranging from about 0.2 meq/gm to about 5 meq/gm,preferably at least about 0.4 meq/gm, more preferably at least about 0.6meq/gm, at the pH of intended use of the personal cleansing composition,which pH will generally range from about pH 4 to about pH 9, preferablyfrom about pH 5 and about pH 8.

Nonlimiting examples of cationic deposition polymers for use in thepersonal care composition include polysaccharide polymers, such ascationic cellulose derivatives. Preferred cationic cellulose polymersare the salts of hydroxyethyl cellulose reacted with trimethyl ammoniumsubstituted epoxide, referred to in the industry (CTFA) asPolyquaternium 10 which are available from Amerchol Corp. in theirPolymer KG, JR and LR series of polymers, with a preferred being KG-30M.

Other suitable cationic deposition polymers include cationic guar gumderivatives, such as guar hydroxypropyltrimonium chloride, specificexamples of which include the Jaguar series (preferably Jaguar C-17)commercially available from Rhodia Inc., and N-Hance polymer seriescommercially available from Aqualon.

Other suitable cationic deposition polymers include synthetic cationicpolymers. The cationic polymers suitable for use in the cleansingcomposition herein are water soluble or dispersible, non crosslinked,cationic polymers having a cationic charge density of from about 4meq/gm to about 7 meq/gm, preferably from about 4 meq/gm to about 6meq/gm, more preferably from about 4.2 meq/gm to about 5.5 meq/gm. Theselect polymers also may have an average molecular weight of from about1,000 to about 1 million, preferably from about 10,000 to about 500,000,more preferably from about 75,000 to about 250,000.

The concentration of the cationic polymer in the personal carecomposition ranges from about 0.025% to about 5%, preferably from about0.1% to about 3%, more preferably from about 0.2% to about 1%, by weightof the composition.

A non limiting example of a commercially available synthetic cationicpolymer for use in the cleansing compositions ispolymethyacrylamidopropyl trimonium chloride available under the tradename POLYCARE 133, from Rhodia.

4. Other Optional Ingredients

Other non limiting examples of optional ingredients include benefitagents that are selected from the group consisting of vitamins andderivatives thereof (e.g., ascorbic acid, vitamin E, tocopheryl acetate,and the like); sunscreens; thickening agents (e.g., polyol alkoxy ester,available as CROTHIX from Croda); preservatives for maintaining the antimicrobial integrity of the cleansing compositions; anti-acne medicaments(resorcinol, salicylic acid, and the like); antioxidants; skin soothingand healing agents such as aloe vera extract, allantoin and the like;chelators and sequestrants; and agents suitable for aesthetic purposessuch as fragrances, essential oils, skin sensates, pigments, pearlescentagents (e.g., mica and titanium dioxide), lakes, colorings, and the like(e.g., clove oil, menthol, camphor, eucalyptus oil, and eugenol),antibacterial agents and mixtures thereof. These materials can be usedat ranges sufficient to provide the required benefit, as would beobvious to one skilled in the art.

Method of Use

The personal care compositions of the present invention are preferablyapplied topically to the desired area of the skin or hair in an amountsufficient to provide effective delivery of the product. Thecompositions can be applied directly to the skin or hair or indirectlyvia the use of a cleansing puff, washcloth, sponge or other implement.The compositions may be in the form of a body wash, shampoo,conditioner, moisture rinse, mousse, substrate, etc. The compositionsare preferably diluted with water prior to, during, or after topicalapplication, and then subsequently the skin or hair rinsed or dried off,preferably rinsed off of the applied surface using water or awater-insoluble substrate in combination with water.

The present invention is therefore also directed to methods of cleansingthe skin through the above-described application of the compositions ofthe present invention. The methods of the present invention are alsodirected to a method of providing effective delivery of the desired skinbenefit agent, and the resulting benefits from such effective deliveryas described herein, to the applied surface through the above-describedapplication of the compositions of the present invention.

Compositions of the present invention may deposit at least about 1μg/cm² of said hydrophilic liquid on skin according to the in vivodeposition method when the concentration of the hydrophilic liquid is atleast about 0.5% of the composition, preferably at least about 1% of thecomposition, more preferably at least about 5% of the composition.Compositions comprising less than 0.5% of the hydrophilic liquid mayalso deposit at least about 1 μg/cm² of said hydrophilic liquid.

The present invention may also be useful in rinse-off applications otherthan personal care compositions including pet care, auto care, home careand medical applications.

Method of Making

The personal care compositions of the present invention may be preparedby any known or otherwise effective technique suitable for making andformulating emulsions and dispersions. It is especially effective to useslow mixing techniques for mixing the hydrophilic liquids with astructurant, mixing the structured hydrophilic liquid with a surfaceactive, and then mixing with the lipid. Non-limiting mixing techniquesinclude hand mixing or mixing with mechanical mixers. For associationstructure forming compositions, it may be necessary to allow thestructured hydrophilic liquids to sit for a few hours to form thestructures. Higher speed mixing is used for mixing the lipid phase withthe aqueous phase. Generally, the compositions are prepared at ambienttemperature/room temperature. The association structure forming processwill depend on the physical state of the surface active. If the surfaceactive is a solid or semisolid at ambient temperature, it may be heatedto melt and mixed with the hydrophilic liquid and allowed to cool toambient temperature.

Analytical Methods

1. Lipid Rheology Method

Lipid rheology is measured on a TA Instruments AR2000 stress-controlledrheometer with a Peltier temperature controlled sample stage or anequivalent. A parallel plate geometry is used with a 40 mm plate and a 1mm gap. The lower plate is heated to 85° C. and the melted lipid andstructurant (if present) is added onto the lower plate and allowed toequilibrate. The upper plate is then lowered to the 1 mm gap whileensuring the lipid fills the gap fully, [spinning the top plate andadding more lipid to promote wicking], and the sample is cooled quicklyto 25° C. and equilibrated at 25° C. for 5 minutes. Viscosity is thenmeasured using a stress-ramp procedure common on these types of machinesusing a logarithmic stress ramp from 20 to 2000 Pa at a rate of 60seconds per decade (2 minute ramp test), with 20 measurements points perdecade. The starting and ending stress is sufficient to induce flow andreach a shear rate of at least 10 sec−1. Viscosity is recorded and thedata fitted to a power law model using Equation 1. Only points between0.001 sec−1 and 40 seconds−1 are to be used in the power law fit. Theviscosity at 1.0 sec−1 is calculated from Equation 1. One shouldcarefully watch the sample during the test so that when the material isejected from under the plate, the method is stopped.

Viscosities are recorded and the data fit to a power law with thefollowing Equation 1:η=κ·γ(dot)^((n−1))where η=viscosity, κ is the consistency and γ (dot) is the shear rate,and n is the shear index.The viscosity at 1 sec−1 is then calculated using the calculated valuesof κ and n from the fitted data.

2. Stability Agent Viscosity Test

Polymeric stabilizer phase is formed using the ratio of stabilizer towater that will be found in the particular formulation of interest. Forexample, if the formulation contains 3 parts stabilizing polymer and 72parts water, the ratio will be 1:24. The polymer is hydrated in thewater phase at the appropriate ratio. The method of hydration will varydepending upon the polymer type, and may require high shear, heating,and/or neutralization. In any event, the polymer should be properlyhydrated according to manufacturer's instructions. Once the polymer isfully hydrated, the system is allowed to sit at room temperature for atleast 24 hours. After the resting period, the viscosity of thestabilizer phase is measured with a Brookfield or similar viscometerusing a cone and plate (Spindle 41 for a Brookfield model DV II+)geometry at 1 sec−1 and 25° C. 2 ml of the product is placed in the cupof the viscometer and attached to the unit. The rotation is started andafter 2 minutes the viscosity is recorded.

3. Lather Volume

Lather volume of a personal care composition can be measured using agraduated cylinder and a tumbling apparatus. A 1,000 ml graduatedcylinder is chosen which is marked in 10 ml increments and has a heightof 14.5 inches at the 1,000 ml mark from the inside of its base (forexample, Pyrex No. 2982). Distilled water (100 grams at 23° C.) is addedto the graduated cylinder. The cylinder is clamped in a rotating device,which clamps the cylinder with an axis of rotation that transects thecenter of the graduated cylinder. One gram of the total personal carecomposition is added into the graduated cylinder and the cylinder iscapped. The cylinder is rotated at a rate of 10 revolutions in about 20seconds, and stopped in a vertical position to complete the firstrotation sequence. A timer is set to allow 30 seconds for the latherthus generated to drain. After 30 seconds of such drainage, the firstlather volume is measured to the nearest 10 ml mark by recording thelather height in ml up from the base (including any water that hasdrained to the bottom on top of which the lather is floating).

If the top surface of the lather is uneven, the lowest height at whichit is possible to see halfway across the graduated cylinder is the firstlather volume (ml). If the lather is so coarse that a single or only afew foam cells (“bubbles”) reach across the entire cylinder, the heightat which at least 10 foam cells are required to fill the space is thefirst lather volume, also in ml up from the base. Foam cells larger thanone inch in any dimension, no matter where they occur, are designated asunfilled air instead of lather. Foam that collects on the top of thegraduated cylinder but does not drain is also incorporated in themeasurement if the foam on the top is in its own continuous layer, byadding the ml of foam collected there using a ruler to measure thicknessof the layer, to the ml of foam measured up from the base. The maximumfoam height is 1,000 ml (even if the total foam height exceeds the 1,000ml mark on the graduated cylinder). One minute after the first rotationis completed, a second rotation sequence is commenced which is identicalin speed and duration to the first rotation sequence. The second lathervolume is recorded in the same manner as the first, after the same 30seconds of drainage time. A third sequence is completed and the thirdlather volume is measured in the same manner, with the same pausebetween each for drainage and taking the measurement.

The lather result after each sequence is added together and the TotalLather Volume determined as the sum of the three measurements, in ml.The Flash Lather Volume is the result after the first rotation sequenceonly, in ml, i.e., the first lather volume.

4. Contact Angle Method

Use a hydrophobic [polyethylene terephthalate (PET)] and hydrophilic[aluminum foil] surface to evaluate the wettability of a given substanceon either substrate. Determine the static contact angles on a flat,smooth, clean piece of either aluminum foil (UHV Foil from All Foils) orPET (Scotchpak 1022 from 3M) 3 times with Millipore Milli-Q pluspurified distilled water and 99% pure diiodomethane (Sigma Aldrich) in aconstant temperature (25±1 C) and constant humidity (relative humidityof 45±2%) clean room (positive pressure, air filtered). The contactangle method is described below. Determine the contact angles of waterand diiodomethane (DIM) (1) on flat, smooth pieces of aluminum foil andPET from pieces carefully removed from the packaging withoutcontaminating the surfaces; (2) after rinsing the pieces 3 times withMillipore purified distilled water and blow drying with ultra-pure(99.999%) nitrogen gas; and (3) after rinsing pieces 3 times with 99%pure toluene and blow drying with ultra-pure nitrogen gas. The Pet oraluminum foil is clean if all three determinations of contact angleagree to the following: (1) on PET: greater or equal to 88° for waterand less than or equal to 45 for DIM and (2) on Aluminum Foil: less thanor equal to 41° for water and greater than or equal to 39° for DIM, and(3) there is no more than a 2-3 degree variance in the 3 sets of pooledmeasurements on PET or aluminum foil. The surfaces of the aluminum foiland PET must be flat, smooth, chemically inert (does not dissolve, swellwithin 30 minutes when in contact with liquids being tested), andchemically homogeneous (functional groups are uniformly dispersed acrosssurface).

Use a Dynamic Contact Angle Analyzer (FTÅ 200, First Ten Angstroms,Portsmouth, Va.). Use the equipment in a clean room kept at 25±1 degreeC. and 45±2% relative humidity on a vibration free bench. Load Milliporepurified distilled water or 99% pure diiodomethane in aseptic chemicallyuncontaminated 10 mL syringes with a 27 gauge aseptic, non-chemicallycontaminated stainless steel blunt tip needles. Mount the syringe in thevertical position with the needle pointing down. Dangle 7±1 μL of wateror 4±1 μL of DIM from the tip of the needle using the pump controls ofFTÅ 200. Carefully lay a flat, smooth piece of PET or aluminum foil onthe z-stage directly below the needle. Use the z-stage to carefully andslowly raise the surface of the PET or aluminum foil until it gentlytouches the bottom of the dangling drop. Illuminate the rear light to80%. Acquire a focused image of the drop at a 3 degree incline (lookdown) to the plane of the PET or aluminum foil. Acquire the image afterthe drop equilibrated (stopped spreading on the surface) or at 30minutes for the highly viscous materials (>20,000 cSt). Determine anaspherically fitted contact angle for both sides of the drop. Report theaverage value for both sides. Repeat the contact angle determinations 3times on separate sections of aluminum foil or PET for each compoundtested. TABLE 1 Examples of contact angles of compounds determined onaluminum foil and PET. Contact Angle (degrees) Compound Aluminum FoilPET Lecithin 20.3 18.9 Abil EM 90 10.9 18.5 Silicone 200 Fluid, 5,000cSt 11.6 27.7 Silicone 200 Fluid, 330,000 cSt 28.3 36.0 AminosiliconeTSF 4707 14.8 17.8 Isopropyl myristate 13.8 13.2

If the material exiting the needle does not form a drop but retains theshape of the orifice of the needle, then the material is spread into aneven, smooth, thick (1-2 mm) film on a glass microscope slide. 4 μL of99% pure DIM and 7-μL Millipore purified distilled water are applied tothe film in a manner identical to the method describing thedetermination of contact angles on PET or aluminum foil above. Staticcontact angles for DIM and water spreading on the films are determinedafter the fluids have stopped spreading—usually within 30 seconds.

5. In-Vivo Deposition Method for Hydrophilic Actives

Method for measuring hydrophilic actives on skin—apply productcontaining hydrophilic benefit agent (analyte) to the inner forearmaccording to the following procedure:

Rinse the forearm from the elbow to the wrist for 5 seconds using 35° C.city water at a flow rate of 50-60 mL/sec. Apply 1.0 mL of liquid soapor the lather from a wetted soap bar rotated in both hands for 6 fullrotations to the entire inner forearm using 10 full back and forthstrokes. Rinse the lather from the forearm for 10 seconds. Rub 1.0 mL ofproduct onto the inner forearm for 10 seconds. Leave the product on theforearm for 10 seconds. Rinse the forearm with water for 10 seconds.Gently pat the forearm dry with a clean, dry paper towel.

Recover deposited analyte from the forearm by using the followingtape-stripping procedure. Firmly place D-Squame tape (22-mm diameter,CuDerm Corporation) on the inner forearm at least 2 inches from theelbow crease. Remove the tape strip with clean Teflon-coated tweezersand place in its own individual pre-labeled container (e.g., adisposable petri dish) with the adhesive side of the tape facing up.Place subsequent tapes firmly on the same spot and collect in the samemanner until a total of 10 tapes are collected per site. Extractadditional areas and pool if necessary to meet the sensitivity limits ofthe chromatography or electrophoretic method.

Use extraction solvent(s) to quantitatively extract (greater than orequal to 95% recovery) the analyte from the tape. Use either (1) asingle solvent or solution of miscible solvents to extract the analytefrom the 10 tapes pooled in a container without also extractingcomponents from the adhesive which interfere with the analyte orinternal standard bands in the chromatography or electrophoresis or (2)use 2 or more immiscible solvents or solutions of solvents which bothextract the analyte from the tape and partition the analyte in a phaseseparate from the components of the adhesive that interfere with theanalyte or internal standard bands used in the chromatography orelectrophoresis described below. Employ sonication or vibration toimprove analyte extraction. If the analyte is not lost or decomposed,several collection sites can be pooled and concentrated by evaporationat ambient, sub-ambient, or elevated temperature with or without avacuum, or with or without a greater than or equal to 99.999% pure gasblow down in order to increase the total amount of analyte recovered.

Use a chromatography or capillary electrophoretic system withappropriate detector that produces adequate sensitivity (signal to noiseratio greater than or equal to 10 for analyte levels at the levelsextracted from skin) and selectivity (baseline resolution, or nomass/charge band overlap or no radioactive countinginterference—depending on the type of detector employed) between theanalyte or internal standard bands and other bands associated with thecomponents from the skin, tape strip adhesive, or product in order toaccurately quantitate the analyte (greater than or equal to 95%confidence limit) when the instrument is functioning properly (passessystem suitability criteria from the manufacturer's operatinginstructions or the current USP (U.S. Pharmacopeia) for chromatographicmethods). Sensitivity for the analytes should be 80-120% of the levelsdeposited on the skin. Internal standards are compounds with similarchemical and physical properties to the hydrophilic benefit agent(s)which (1) do not coelute or interfere with mass/charge bands orinterfere with the radioactive counting of the hydrophilic benefit agentbands; and (2) elute close to the hydrophilic benefit agent bands.Proper functioning would also produce the following 2 conditions ifpresent in the chromatographic or electrophoretic system: (1) The % RSD(relative standard deviation) of the retention time is less than orequal to 2.0% for six sequential injections of the analyte(s) andinternal standard; and (2) a minimum correlation coefficient betweenanalyte band response (normalized to internal standard) andconcentration of analyte of 0.99 for a minimum of 5 point externalcalibration curve. Two examples of chromatographic methods are givenbelow:

EXAMPLE 1 Glycerin as the Hydrophilic Benefit Agent

Add 1 mL of 0.01 N aqueous H₂SO₄ and 9 mL methanol to the containercontaining the tape strips, vortex for 1 minute, sonicate for 10minutes, allow to stand for 30 minutes, and filter using a 0.45 μm poresyringe filter. Concentrate the filtrate using a gentle nitrogen purgeto 1 mL total volume. Use a high performance liquid chromatography(HPLC, Model 2595, Waters Corp., Milford, Mass.) with a differentialrefractometer detector (Model 2414, Waters Corp.) employing thefollowing conditions: IOA-1000 column (300 mm×7.8 mm, AlltechAssociates, Inc, Deerfield, Ill.) at 65° C. with an isocratic flow rateat 0.6 ml min⁻¹ of 0.01 N aqueous H₂SO₄ and 10 μL injection volume.

EXAMPLE 2 Dihydroxyacetone as the Hydrophilic Benefit Agent

Add 1 mL of 0.005 N aqueous H₂SO₄ and 9 mL methanol to the containercontaining the tape strips, vortex for 1 minute, sonicate for 10minutes, allow to stand for 30 minutes, and filter using a 0.45 μm poresyringe filter. Concentrate the filtrate using a gentle nitrogen purgeto 1 mL total volume. Use an HPLC (Model 2595, Waters Corp.) with adifferential refractometer detector (Model 2414, Waters Corp.) employingthe following conditions: IOA-1000 column (300 mm×7.8 mm, AlltechAssociates, Inc.) at 65° C. with an isocratic flow rate at 0.6 ml min⁻¹of 0.005 N aqueous H₂SO₄ and 40 μL injection volume.

6. Identification of Association Structures

Association structure formation may be identified using one or more ofseveral identification techniques. The onset of association structureformation and the occurrence of a substantially one phase liquid crystalstate for a particular surface active and hydrophilic liquid system canbe identified by: 1) visual observation with the naked eye; 2)birefringent optical activity observed by polarized light microscopy; 3)measurement of the surface active/hydrophilic liquid system NMR spectra;4) measurement of apparent viscosity profile; 5) presence of acharacteristic “texture” pattern observable under cryo Scanning ElectronMicroscopy (cryo-SEM) and/or Freeze-Fractured Transmission ElectronMicroscopy (FF-TEM); 6) x-ray diffraction. These methods are describedin more detail in U.S. Pat. No. 5,599,555.

NON-LIMITING EXAMPLES

The compositions illustrated in the following Examples exemplifyspecific embodiments of the compositions of the present invention, butare not intended to be limiting thereof. Other modifications can beundertaken by the skilled artisan without departing from the spirit andscope of this invention. These exemplified embodiments of thecomposition of the present invention provide enhanced deposition of thepersonal care composition. The compositions illustrated in the followingExamples are prepared by conventional formulation and mixing methods, anexample of which is described above. All exemplified amounts are listedas weight percents and exclude minor materials such as diluents,preservatives, color solutions, imagery ingredients, botanicals, and soforth, unless otherwise specified.

Examples 1-10

Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ingredientwt % wt % wt % wt % wt % wt % wt % wt % wt % wt % I. Aqueous PhaseComposition Hydroxypropyl 3.5 4.0 3.5 3.5 3.5 3.0 3.5 3.5 3.5 3.5 StarchPhosphate (Structure XL from National Starch) Emulsifying Wax NF 2.753.0 2.75 2.75 2.5 2.75 2.75 2.75 (Polawax from Croda) Behenetrimonium2.25 2.0 methosulfate and cetearyl alcohol (Incroquat Behenyl TMS fromCroda) Fragrance 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Preservatives0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Water Q.S. Q.S. Q.S. Q.S. Q.S.Q.S. Q.S. Q.S. Q.S. Q.S. II. Lipid Composition Petrolatum 12 20 12 14 2415 20 13 20 (Superwhite Protopet from WITCO) Mineral Oil 10 2 13(Hydrobrite 1000 PO White MO from WITCO) III. Structured HydrophilicPhase Composition Dimethicone Fluid 1.2 (Dow Corning Silicone Fluid60,000 cst) Lecithin Thermolec ™ 9.0 10 8 10 200 (ADM SpecialtyIngredients) Monomuls 90 L-12 3.5 1.5 (Cognis Co.) Monomuls 90-O18 3.51.5 3.0 (Cognis Co.) Generol 122 N E-5 3.0 (Cognis Co.) Abil EM 90 9.0(Degussa) Silica Shells (KOBO 1.2 1.0 1.2 products) Hubersorb 600 (J. M.1.5 Huber Corporation) Water Lock G-580 1.2 (Grain ProcessingCorporation Zil Gel SM 8.0 (Presperse Incorporated) Kosher Superol 7.88.1 7.8 7.5 4.2 7.0 7.0 8.0 7.0 Glycerin (Procter & Gamble Co.)Niacinamide 5.5 Water 4.2

Examples 11-12

Ex. 11 Ex. 12 Ingredient wt % wt % I. Aqueous Phase CompositionHydroxypropyl 3.5 3.5 Starch Phosphate (Structure XL from NationalStarch) Emulsifying Wax NF 2.75 2.75 (Polawax from Croda)Behenetrimonium methosulfate and cetearyl alcohol (Incroquat Behenyl TMSfrom Croda) Fragrance 1.0 1.0 Preservatives 0.8 0.8 Water Q.S. Q.S. II.Lipid Composition Petrolatum 20 19 (Superwhite Protopet from WITCO)Mineral Oil (Hydrobrite 1000 PO White MO from WITCO) III. StructuredHydrophilic Phase Composition Generol 122 N E-5 1.1 3.0 (Cognis Co.)Monomuls 90 L-12 3.0 (Cognis Co.) Monomuls 90-O18 2.0 (Cognis Co.)Kosher Superol 1.0 Glycerin (Procter & Gamble Co.) Dihydroxyacetone 5.55.5 (Merck KGaA) Water 3.0 2.1

Prepare the personal care composition of Examples 1-12 by conventionalformulation and mixing techniques.

Prepare the aqueous phase composition by first dispersing thehydroxypropyl starch phosphate in water. Add emulsifying wax and heat to160° F. (71.1° C.). Next, place the mixing vessel in a water bath tocool to under 100° F. (37.78° C.). Add fragrance.

Prepare the structured hydrophilic phase by first premixing thehydrophilic liquid with the structurant if necessary (i.e. not alreadypre-mixed by the supplier). Mix the mixture with the surface active.

Mix the structured hydrophilic phase with the lipid. If the lipid is asolid or semi-solid, it is preferable to add the internal structuredhydrophilic phase to melt lipid.

Add the premix of the lipid phase to the aqueous phase and mix viaconventional mixing techniques.

Examples 13-14

Ex 13 Ex 14 Ingredient wt % wt % I. Cleansing Phase Composition MiracareSLB-365 (from Rhodia) 47.4 47.4 (Sodium Trideceth Sulfate, SodiumLauramphoacetate, Cocamide MEA) Guar Hydroxypropyltrimonium Chloride 0.70.7 (N-Hance 3196 from Aqualon) PEG 90M (Polyox WSR 301 from DowChemical) 0.2 0.2 Sodium Chloride 3.5 3.5 Preservatives 0.84 0.84 CitricAcid 0.4 0.4 Perfume 2.0 2.0 Expancel 091 DE 40 d30 (from Expancel,Inc.) 0.4 0.4 Water Q.S. Q.S. (pH) (6.0) (6.0) II. Lipid CompositionPetrolatum (Superwhite Protopet from WITCO) 62.4 62.4 Mineral Oil(Hydrobrite 1000 PO White MO from WITCO) 20.8 20.8 III. Structuredhydrophilic phase composition Lecithin Thermolec ™ 200 (ADM SpecialtyIngredients) 8.0 Silica Shells (KOBO products) 1.0 Monomuls 90 L-12(Cognis Co.) 3.5 Monomuls 90-O18 (Cognis Co.) 3.5 Kosher SuperolGlycerin (Procter & Gamble Co.) 7.8 10.0

Prepare the composition described above by conventional formulation andmixing techniques. Prepare the cleansing phase composition by firstadding citric acid into water at a 1:3 ratio to form a citric acidpremix. Add the following ingredients into the main mixing vessel in thefollowing sequence: water, Miracare SLB-354, sodium chloride, andpreservatives. Start agitation of the main mixing vessel. In a separatemixing vessel, disperse polymer (N-Hance 3196) in water at 1:10 ratio toform a polymer premix. Add the completely dispersed polymer premix intothe main mixing vessel with continuous agitation. Disperse PEG 90M(Polyox WSR 301) in water and then add to the main mixing vessel. Then,add the rest of the water, perfume, and Expancel into the batch. Keepagitating until a homogenous solution forms.

Prepare the structured hydrophilic phase by first premixing thehydrophilic liquid with the structurant if necessary (i.e. not alreadypre-mixed by the supplier). Mix the mixture with the surface active.

Prepare the lipid phase by adding petrolatum into a mixing vessel. Heatthe vessel to 190° F. (87.78° C.). Then, add mineral oil with agitation.Add the structured hydrophilic phase with agitation.

The cleansing and lipid phases are density matched to within 0.05 g/cm³.Package both phases into a single container using conventionaltoothpaste-tube filler equipment. The sample stage spins the bottleduring filling process to create a striped appearance. The stripe sizeis about 6 mm in width and 100 mm in length.

Example 15

Ingredient wt % I. Phase 1 Ammonium Laureth-3 Sulfate (25% Active) 46.7Citric Acid Anhydrous 1.76 Sodium Lauroamphoacetate (27%) 43.47Trihydroxystearin (Thixcin R from Rheox) 2.35 Preservatives 1.73 LauricAcid 2.35 Petrolatum 1.64 II. Phase 2 Ammonium Laureth-3 Sulfate 18Ammonium Lauryl Sulfate (25% Active) 12 Phase 1 42.6 Fragrance 1.0Premix 1 Guar Hydroxypropyltrimonium Chloride 0.3 (N-Hance 3196 fromAqualon) Water QS Premix 2 Petrolatum 15 Monomuls 90-O18 (Cognis Co.) 4Kosher Superol Glycerin (Procter & Gamble Co.) 7

Prepare the composition described above by conventional formulation andmixing techniques. Prepare phase 1 by first adding citric acid into theammonium laureth-3 sulfate. Once the citric acid is full dissolved, addthe sodium lauroamphoacetate. Heat the mixture to 190-195° F.Incorporate the trihydroxystearin fully and then add preservatives.Continue to mix as petrolatum is added. Prepare phase 2 in a separatemixing vessel. Add ammonium laureth-3 sulfate then ammonium laurylsulfate to mixing vessel in a water bath. To this vessel add Phase 1with continuous mixing. Premix the guar hydroxypropyl trimonium chlorideand water (Premix 1). Add Premix 1 to mixing vessel. Prepare premix 2 bymixing petrolatum and the premix of Monomuls 90-O18 with glycerin in aseparate mixing vessel. Heat the vessel to 190° F. Then, add Premix 2 toPhase 2. Then add perfume. Keep agitating until a homogenous solutionforms.

Examples 16-18

Example Example Example 16 17 18 Ingredient wt % wt % wt % I. AdditionalAqueous Phase Composition Miracare SLB-365 (from Rhodia) 47.4 47.4 47.4(Sodium Trideceth Sulfate, Sodium Lauramphoacetate, Cocamide MEA)Cocamide MEA 3.0 3.0 3.0 Guar Hydroxypropyltrimonium 0.7 0.7 0.7Chloride (N-Hance 3196 from Aqualon) PEG 90M (Polyox WSR 301 from 0.20.2 0.2 Dow Chemical) Glycerin 0.8 0.8 0.8 Sodium Chloride 3.5 3.5 3.5Disodium EDTA 0.05 0.05 0.05 Glydant 0.67 0.67 0.67 Citric Acid 0.4 0.40.4 Perfume 2.0 2.0 2.0 Red 7 Ca Lake 0.01 0.01 0.01 (From LCW) WaterQ.S. Q.S. Q.S. (pH) (6.0) (6.0) (6.0) II Aqueous phase compositionAcrylates/Vinyl Isodecanoate 1.0 1.0 1.0 Crosspolymer (Stabylen 30 from3V) Xanthan gum 1.0 1.0 1.0 (Keltrol CGT from CP Kelco) Triethanolamine1.5 1.5 1.5 Sodium Chloride 3.5 3.5 3.5 Glydant 0.37 0.37 0.37 Water andMinors Q.S. Q.S. Q.S. (pH) (6.0) (6.0) (6.0) III. Lipid CompositionPetrolatum (Superwhite Protopet 10 10 from WITCO) Mineral Oil(Hydrobrite 1000 PO 15 White MO from WITCO) III. Lipid CompositionPetrolatum (Superwhite Protopet 10 10 from WITCO) Mineral Oil(Hydrobrite 1000 PO 15 White MO from WITCO) IV. Structured Hydrophilicphase Composition Monomuls-90-O18 (Cognis Co.) 3.5 2.0 3.0 Monomuls90-L12 (Cognis Co.) 3.5 3.0 Kosher Superol Glycerin (Procter & 7.0 5.07.0 Gamble Co.) Niacinamide 5.5

The compositions described above can be prepared by conventionalformulation and mixing techniques. Prepare the additional aqueous phasecomposition by forming the following premixes: add citric acid intowater at 1:1 ratio to form a citric acid premix, add polyox WSR-301 intoglycerin at 1:3 ratio to form a polyox-glycerin premix, and add cosmeticpigment into glycerin at 1:20 ratio to form a pigment-glycerin premixand mix well using a high shear mixer. Then, add the followingingredients in the main mixing vessel in the following sequence: water,N-Hance 3196, polyox premix, citric acid premix, disodium EDTA, andMiracare SLB-365. Mix for 30 minutes, then begin heating the batch toapproximately 49 degrees C. Add CMEA and mix until homogeneous. Then,cool the batch to ambient temperature and add the following ingredients:sodium chloride, glydant, cosmetic pigment premix and perfume. Mix thebatch for 60 minutes. Check pH and adjust pH using citric acid orcaustic solution if needed.

Prepare the structured hydrophilic phase by first premixing thehydrophilic liquid with the structurant if necessary (i.e. not alreadypre-mixed by the supplier). Mix the mixture with the surface active.

Mix the structured hydrophilic phase with the lipid. If the lipid is asolid or semi-solid, it is preferable to add the structured hydrophilicphase to the lipid.

Add the premix of the lipid phase to the aqueous phase and mix viaconventional mixing techniques.

Prepare the aqueous phase by slowly adding Stabylene 30 into water withcontinuous mixing. Then, add Keltrol CG-T. Heat the batch to 85 degreesC. with continuous agitation. Then, add lipid phase containing thestructured hydrophilic phase. Cool down the batch to ambienttemperature. Then, add Triethanolamine. Add sodium chloride, glydant andmix until homogeneous.

The aqueous phase and the additional aqueous phases can be combined byfirst placing the separate phases in separate storage tanks having apump and a hose attached. Then, pump the phases in predetermined amountsinto a single combining section. Next, move the phases from thecombining sections into the blending sections and mix the phases in theblending section such that the single resulting product exhibits adistinct pattern of the phases, including but not limited to, striped,marbled, geometric, and mixtures thereof. Next, pump the product fromthe blending section via a hose into a single nozzle, then place thenozzle into a container and fill the container with the resultingproduct. The stripe size is about 6 mm in width and 100 mm in length.The products remain stable at ambient for at least 180 days.

All documents cited in the Background, Summary of the Invention, andDetailed Description of the Invention are, in relevant part,incorporated herein by reference; the citation of any document is not tobe construed as an admission that it is prior art with respect to thepresent invention. To the extent that any meaning or definition of aterm in this written document conflicts with any meaning or definitionof the term in a document incorporated by reference, the meaning ordefinition assigned to the term in this written document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A personal care composition comprising: a) a hydrophilic liquid; b) astructurant for said hydrophilic liquid; c) a surface active; d) alipid; and e) an aqueous phase, wherein said lipid, said hydrophilicliquid, said structurant, and said surface active form a lipid phase;wherein said hydrophilic liquid, said structurant, and said surfaceactive are on the surface of said lipid, within the domain of saidlipid, or both on the surface and within the domain of said lipid insaid lipid phase.
 2. The personal care composition of claim 1 whereinsaid structurant is selected from the group consisting of associationstructure forming materials, fluid absorbent particles, inorganicparticulate thickeners, and water-soluble or water-swellable polymers.3. The personal care composition of claim 1 wherein said structurant isselected from the group consisting of fluid absorbent particles,inorganic particulate thickeners, and water-soluble or water-swellablepolymers.
 4. The personal care composition of claim 1 wherein saidsurface active is selected from the group consisting of associationstructure forming materials and film forming materials.
 5. The personalcare composition of claim 4 wherein said association structure formingmaterials form association structures selected from the group consistingof micelles, reverse micelles, lyotropic liquid crystals, and mixturesthereof.
 6. The personal care composition of claim 4 wherein saidassociation structure forming materials are selected from the groupconsisting of anionic, cationic, nonionic, amphoteric surfactants,alkoxylated polymers, polysaccharides, silicone copolyols, andaminosilicones.
 7. The personal care composition of claim 4 wherein saidfilm forming materials are selected from the group consisting ofdialkylquates, ester oils, silicone oils, silicone waxes, liquid fattyalcohols and fatty acids, and microfine particles.
 8. The personal carecomposition of claim 1 wherein said structurant and said surface activeare both association structure forming materials.
 9. The personal carecomposition of claim 1 wherein said hydrophilic liquid is present in anamount of from about 0.1% to about 90% by weight of the composition. 10.The personal care composition of claim 1 wherein said lipid phase ispresent in an amount of from about 1% to about 95% by weight of thecomposition.
 11. The personal care composition of claim 1 wherein theratio of said structurant to said hydrophilic liquid is from about1:1000 to about 100:1.
 12. The personal care composition of claim 1wherein the ratio of said surface active to said hydrophilic liquid isfrom about 1:1000 to about 20:1.
 13. The personal care composition ofclaim 1 wherein the combination of said hydrophilic liquid and saidstructurant form a material having a viscosity of at least about 3000cst at 25° C.
 14. The personal care composition of claim 1 wherein saidlipid phase is one visually distinct phase that is packaged in physicalcontact with said aqueous phase while maintaining stability.
 15. Thepersonal care composition of claim 1 further comprising an additionalaqueous phase that is a visually distinct phase that is packaged inphysical contact with said composition while maintaining stability. 16.The personal care composition of claim 15 wherein said additionalaqueous phase further comprises a surfactant.
 17. The personal carecomposition of claim 1 further comprising an optional ingredientselected from the group consisting of structurant for aqueous phase,surfactant, and cationic polymers.
 18. The personal care composition ofclaim 1 wherein said composition deposits at least 1 μg/cm² of saidhydrophilic liquid on skin according to the in-vivo deposition methodwhen the concentration of said hydrophilic liquid is at 5.0% of saidpersonal care composition.
 20. A personal care composition comprising:a. a hydrophilic liquid; b. a structurant for said hydrophilic liquid;c. a surface active; and d. a lipid wherein said lipid, said hydrophilicliquid, said structurant, and said surface active form a lipid phase;wherein said hydrophilic liquid, said structurant, and said surfaceactive are within the domain of said lipid in said lipid phase; whereinsaid structurant is selected from the group consisting of fluidabsorbent particles, inorganic particulate thickeners, and water-solubleor water-swellable polymers.
 21. A method of encapsulating activeingredients by: a) combining a surface active and a hydrophilic liquidto form an association structure; b) dispersing said associationstructure in a lipid phase; and c) dispersing said lipid phase inaqueous phase.
 22. A method of delivering hydrophilic benefit agents toskin or hair, said method comprising the steps of: dispensing aneffective amount of the personal care composition according to claim 1directly onto skin or hair or indirectly onto skin or hair via animplement selected from the group consisting of a cleansing puff,washcloth, and sponge and removing said composition from skin and/orhair by rinsing with water.